Processes for the preparation of new carbohydrate compounds and products thereof



March 9, 1954 sans VER Erm. 2.671.780

PROCESSES FOR THE PREP@ ION 0F NE' CARBOHYDRATE communs um nowc'rs 'x1-maso? Qrignal Filed Aug. 3l. 1w 5 Shoah-hiaat 1 s, u b annua/druide "'c an :Yon-Weow'olvent J 25g c cartina topnlu Z'lgmall'al'tmhak n x I HocL'Lc'HcH- (cnofrmou) c'z. l l

s Reaction io pradera radeawtwvbde mdk' Hy'oxde fn How, HfcH- Hummm Meg ,nn-43m... sa/mc Organic harm fofralacez-Jlvanouym' )nolhlcrcbde H0611,y lffclJl-J (cHaMtI/olva'i to t fol 21ml) f a lgfmfmeffmffde "ma Q ETW, z. ,umza rn March 9, 1954 K. M. GAVE Y Pnocssss Foa THE PREPARATI'N; cARBoHYomT'GTlJO cmounns ma moonen-s maar Original Filed Aug. 31. 1948 5 Sheets-Sheet? [gtcrch-l Illkl galli-'oxide n Afan-Iguana: golvepl Yami cMwXc/rogllarozz- A; des (rgowftmr) R ,hn Z-Jbhvfgsa Glue all aa; af {andra/antan? nu ma; ufawtalomfrya 27 uns gi fo ,follia Ilonnl-ryi-exllcllc flgmenf of Matth 9, 1954 K M @AVER Erm, 2,671,780

PROCESSES FOR THE PREPARATION 0F NE' Umm COMPOUNDS AND PRODUCTS mi' ollillll Fildmll. 31, 194B 5 mshiOt 3 :geni-cx 11H0 Eegcfolkto ffvnc 'Monoclllcli lvtlc @cfg {Marg} Mahal-@MM- l [wen me Mam- W llcli H droxl'le in Non-13011.: .blunt Organic HaIJe Reaction to reduce @Non a- Metdlac R'X ognzatc -Manoalkalftcrchde Jal!! 0 7 l 1ra 11, cli/cfm (wail/arm".

gzqflagdgy @94,113 summum fiumi. a ,0n/

Cl to JIJ' tc zu, f y Mmamelllzc arc sneer mfgtigf och', HtcH-Ncoyclfo/I) di Kondensation De radatan 0 z datzfon Reduction ,ttm

eplament o dni an Graaf-r ofMultz'ple V'dlen t D exm tives IJ'I'HII P. Idil/ll' March 9, 1954 PROCESSES FOR 'l1-IE PREPARATION 0F M. GAVER Er 71,780

NEWC

COIPOUNDS AND PRODUCTS THEREOF Original Filed Aug. 31. 1948 5 Smets-Sheet 4 'l Hike/l' Mufa n Ahn-queens .Salaam ma. ',wmmmaawwmfe Mory u' Hztmav-)fclaumvmc znm/iz's'f" I lkadzzan fa we Z'Mnnol l Emilia 2 3" .cnrgan c Sfar-:Mie

mim-Xeligwcwcmim-m I Er''afm. cial Mela/lic Sal? Subsh'laftwr Hanfan ft miga-)mammu- 5' l Re im of fw '312.

oa we.:

KENNETH M. MVM lRK .UHZSZZIY .ESI'HZR P. MSI/Rl INVEWDRS Y at. ,44

March 9, 1954 K. M. GAVER Erm. 2,671,780

Paocsssas ron ma Pammnon oF um cmaomm'm couPouuns mn Paouuc'rs 11mm? Original Filed Aug. 31. 1948 5' Sheen-Sheet 5 Sla ds/:,Zaldzlgo/vd Reac'an (o prgduce 6- "gg Mmoaaalf .fem/wfg, Mgg f H'' uomgcmcH-twawf'lnw4o- Mm-M15- H( A l H f l md Wafer c mzrawcofm '55 a "M macmcwvfcmma'- R awemenf 44 l'o ups afm( cva en Duufcnl't'nave'- al "H lf HHHydml'nfaT-uab .S'ggg :ein :zzgl-" ic MvmmlqC-al Glaces' f--sfz e nbc!! clima/:Mmmm Mmmm( gf g'oa Y .s u'a on nl. nuff c d 5M Es erl'll''agzn efr. KZNJYZTHM. VIR

pm unw ESTHZRINI; Fig. 5.

3y yum 0f. jg(

T cir Affari: v

Mlre 9' Kenneth M. Gaver, Columbus, Ohio, Derk V.

Tieszen, Delmar, N. Y., and Esther P. Lasnrek Grove Gity, Ohio, assiguors to The Ohio State University Research Foundation, Columbus, hio, a corporation of Ohio Original application August 31, 1948, Serial No. 634,328. Divided and this application January 16, 1851, Serial No. 206,258

1 15 Claims. (0l. i60-233.3) 2

This application is a division of our copending Cent. 2: 1761. (1928)) produced a monoalkali application Serial Number 694,323, filed August derivative of starch by treating the starch with 31, 1946 now Patent 2,609,370. an alkali metal in liquid ammonia. Either as a The inventions disclosed in this application final product or as an intermediate product these relate to new compositions of matter or lcom- 5 investigators obtained a monoalkali compound pounds and to new processes for the formation in which it was concluded that the reaction ocof a large number of such new compounds which curred on the six position carbon in the glucose have been heretofore unknown. The processes unit of the starch molecule. Other investigators described herein illustrating our invention are obtained sodium hydroxide adsorption comespecially designed to produce new products from pounds by dissolving starch in aqueous alkali folstarch and ordinarily include as one of the steps lowed by alcohol precipitation or by treating the hydrolysis of an intermediate compound to starch with alkali metal alcoholates. These produce a" glucoside, a glucose, or similar comcompounds, however, were not starchates in that pound. the alkali metal did not enter into the starch In carrying out preferred embodiments of our molecule. process. we produce as intermediate products Likewise, if glycogen, inulin, etc. are treated in certain new compounds which we have discovered liquid ammonia with an alkali metal, a monoaland synthesized by our processes; these interkali derivative is formed which is similar to the mediate products in the nature of alcoholates of ammonia. process starchates referred to in the starch. To designate these compounds, we have last paragraph. This monoalkali derivative difcoined the word "stai-chate" which we denne fers essentially from the monoalkali derivative as follows: Starchate means and is used in formed in the process described in application this specification and in the claims hereof in the Serial No. 707,315, now Patent 2.516.135 in that sense of a compound composed of an undeterthe alkali metal in such ammonia process mined number of polymerized glucopyranose umts starchates is attached to the No. 6 carbon atom wherein one or more'metallic atoms or inorganic whereas in the monoalkali starchate described or organic radicals are substituted for the hydroin such prior application and described herein gen atoms oi' one or more of the several hydroxyl in connection with many of the processes of our groups of the starch unit so as to form a polypresent inventions is one in which the alkali merized compound which in fact is (or is at metal is attached to the No.2 carbon atom. least analogous to) an alcoholate ot starch. Heretofore as stated above, it has been possible Prior to our invention disclosed herein a cerby known processes to form compounds in which tain process had been discovered for the submetallic and non-metallic elements, organic radistitution of alkaline metals in the starch molecule calsl and/or other groups are substituted for one to form a starchate which we will refer to hereor more hydrogen atoms of one of the hydroxyl inafter as the ammonia process and the ammonia groups of a glucose or similar sugar. However, process stai-chate. in the prior art proc dealing with starch it Also, according to prior art methods, mono has not been possible heretofore to accurately and poly-substituted products of cellulose and predetermine on which of the hydroxyl groups of simple sugars had been prepared, as for exthese substituted groups might be placed nor has ample, asdescribed in Scherer and Hussey, Jourit been possible to form compounds in which nal of American Chemical Society, 53: 2344, selected predetermined groups are substituted 1931); Schorigin et al., Berichte 69: 1713 (1936): on the various hydroxyl carbon atoms nor to Peterson and Barry, U. S. Patent 2,157,083, 1939: form compounds which have one group subunknown British Patent 463,056 (1937); Muskat, stituted on one carbon atom. a second group on Journal of American Chemical Society, 56: 693 a second carbon atom and a third group on a (1934) and Muskat. Journal of American Chemithird carbon atom. We can, by our new processes. cal Society, 56: 2449 (1934). A! will be dmonform auch compounds, strated hereafter in this application, these subune of the objts of 0mmvention is the pro.. stltuted products 0f ellulse and 0I Sugars are 50 vision of new and useful processes of forming new diiferent from the products produced by our imand useful carbohydrates from starch. proved process. Referring again to the prior art A further object oi' our invention is the proprocess designated above as the "ammonia vision of new and useful processes for forming process, it may be noted that Schmid et al. various new products from starch. (Chemical Abstracts 20: '144 (1926) and Chem. A further object of our invention is the provision of new and useful proc for forming various new and old glucoses and glucosides.

A further object of our invention is the provision oi' a new and useful process of forming polysubstituted products from starch.

A further object of our invention is the provision of new and useful products formed from starch.

Further objects and features of our invention will be apparent from a reading of the subjoined specification and claims when considered in connection with the accompanying drawings showing several exemplary processes illustrating certain embodiments of our inventions.

In the drawings:

Fig. l is a diagram illustrating a process of forming monoalkali starchates, monoorganic starchates, starchates having one or more organic radicals and an alkali group substituted on the same gluco pyranose unit, polyorganic starchates, glucoses, glucosides, glucose derivatives, and glucoside derivatives;

Fig. 2 is a similar diagram illustrating alternative processes to form the same and similar products and also illustrating alternative steps by which monoorganic glucoses and glucosides and their derivatives. and nonalkali monometallic starchates and mixed organic and metallic starchates and derivatives thereof may also be formed:

Fig. 3 is a similar diagram illustrating alternative similar processes for producing the same and similar products, the first step of which comprises the process of making ammonia process starchates:

Fig. 4 is a similar diagram illustrating alternative processes for producing similar products and disclosing among other new processes, new processes of producing mono and diorganic glucoses and glucosides; and

Fig. 5 is a similar diagram illustrating the process of producing 6-monoorganic glucoses and 6-monoorganic a-glucosides and derivatives thereof.

In co-pendlng application Serial No. 357,995 now abandoned and in the continuations thereof, there are disclosed inventions relating to monometallic starchates (both alkali and nonalkali). to monoorganic starchates, and to methods for their preparation.

In co-pending application Serial No. 707,318, now Patent 2,518,135, there are disclosed inventions relating to monoalkali metal starchates, methods for their preparation, and derivatives thereof. The inventions so disclosed are based upon the discovery that when starch is reacted with alcohol soluble hydroxides (such as the hydroxides of lithium. sodium. potassium, rubidium and caesium) under certain conditions there is produced a metallic starchate wherein the alkali metal is attached through an oxygen atom to a carbon atom in the complex-glucopyranose residue (the structure commonly considered as the building unit of starch).

The starchate product formed is a glucopyranose compound. The structural formula of the unit forming the building unit of the complex starchate may be illustrated as follows wherein MA represents an alkali metal:

n socm-n-(cn-Hcaom-(cHoMo-noate (when tested by titration and chemical reactions) definitely proves that the starch derivative formed is not an addition or coordinated compound but is a true alcoholate of starch.

In preparing the 2-monoalkali starchates re- :erred to above. we have investigated the effect of the following factors on the reaction.

Temperatures Any temperature from C. up to 115 C. in an open or closed system, which permits the volatilization of the water produced in the reaction produces 2-monosodium starchate. If the system is closed so that the water evolved in the reaction is retained in the reaction mixture, then the reaction will yield 2-monosodium starchate at any reasonable temperature above 80 C., i. e. up to the dextrinization temperature (unknown in non-aqueous solvents but perhaps to 200 C. or higher). Somewhere above 115 C., in an open system, other reactions occur and the product is no longer Z-monosodium starchate. Under strongly dehydrating conditions. e. g. with alcoholates, this reaction can be driven to completion at temperatures lower than 80 C.

Pressure Apparently there is but very, very slight volume changes occurring in this reaction. Pressures up to 55 lbs. have been used with no eiect on the course of the reaction or upon the product produced by the reaction. It is very probable that any practical pressure may be used provided the temperature and other requirements are not violated.

Time o! reaction The time of reaction varies with the solvent chosen. With ethyl alcohol any time beyond two hours does not alter the course of the reaction nor the character of the product. With butanol, the reaction is complete by the time the butanol (technical grade) reaches the boiling point of 115 C. A generalization may be made in that the reaction is completed within two hours at S30-81 C. or instantaneously at 115 C. or higher regardless oi the nature of the solvent. Any temperature between 80 C. and 115 C. would require a proportionate reaction time (e. g. at C. the time required is about 'l5 min. and at C. the time required is about 15 min., etc).

Alkali concentration It has been repeatedly demonstrated that the reaction is independent of alkali concentration and the same product is always obtained provided there is sumcient alkali present to satisfy the requirements of the product. At the lower temperature range, i. e. 80 C., it is advisable to use an excess of alkali in order to complete the reaction in the two hour period. At the higher temperature range, i. e. C., or higher only an amount of alkali approaching stoichiometric equivalent is necessary. 'I'he mother liquor from the latter reaction always shows a faint alkalinity approximating 0.04 N. This alkalinity apparently arises from the protein-alkali interaction product extracted from the starch. The protein is known to be extracted from the starch and appears in the mother liquor.

Nature ol the alkali Of the alkalies only ammonia failed to react. Sodium and potassium hydroxide. sodium methylate, sodium ethylate, sodium propylate and sodium butylate all yield chemically similar products. Any caustic alkali or alkaline reacting ma.

teriai having an ionization constant of 2x10* or greater will react provided that it is more than very slightly soluble in the chosen reaction media and also provided that lthe ymolecular size ot the reacting molecule is not too large to locate itself in position to react with/@the starch.

Mechanism o! the reaction (CsHioOs) +NaOH- (CsHoCsNa) +H2O 2. Starch readily adsorbs alkalies and such adsorption complexes were isolated and characterized by Karrer. Pringsheim and others. This was veried in our laboratory. At room temperature or even nearly up to 79 C.. either in water. in alcohols or in other solvents exerting some solvent action towards alkalies the following reaction usually occurs:

Such adsorbed alkalies are readily lost to give the adsorption compounds analyzing to be diamylates, triamylates, etc.

Portions of our inventions are based on the fact discovered by us that on heating. in a system which aids the removal oi water either by dilution, by evaporation, or by reaction, this complex can be decomposed into the compound claimed and water as:

As stated above prior hereto this complex had been formed. However. no one had heretofore converted the complex to a starchate. In order to do so. it is n to separate the complex out of the solution (at least remove the water from the complex) and then in heating to 81 C.. make provision for removal of water as stated above either by dilution. evaporation or reaction.

Dilution is obtained by usine solvents; distillation or evaporation removes water from the reaction mixture; and reaction removes water by absorption. For example. by the use of sodium alcoholate the water is removed to produce more alcohol and alkali as:

3. The position of reaction is on C-2. 2-monosodium starchate reacts easily with methyl iodide at temperatures of 80 C. or higher to yield Z-monomethyl starchate.

This Z-monomethyl starchate may then be hydrolyzed to yield 2monomethyl glucose.

4. A substance analyzing to be monosodium starchate may be prepared usingr liquid ammonia and metallic sodium but this compound is difierent and distinct from the one heretofore described as is shown by the following:

NH: ,(CsHwOn) 2N 2(GsBsOsNs) (li-monosodium shrclnte) g.

(CsHsOsCHa) (bmnnnmetliyl shrchatc) Nal CIHIOICHJ N 2CsH1Os(C HshNa (L6-dimethyl, t-monosodlum starchate) H 6.

CsHiOsUJHshNa CHsI 0 CsHiOiwBl): (2.8,6-trimethyl stsrchate) NaI Reaction l above goes only as indicated. In contrast to cellulose and other carbohydrates. starch yields only a monosodium starchate when treated with metallic sodium in liquid ammonia. The position occupied by the sodium was blocked in reaction 2 so that it would not be available ior reaction with the process previously described herein. However, when the product of reaction 2 above was subjected to the reaction previously described herein. the same reaction proceeded smoothly and completely to its limit as indicated in reaction 3 above. The positionoceupied by the sodium of reaction 3 was blocked by methylation in reaction 4. When the product was again subjected to metallic sodium in liquid ammonia (reaction 5 above) a second hydroxyl group is reacted which when methylated yields a trimethyl starch in reaction B above.

If, however, we reverse the order of above reactions we have:

l? C. (CsHloOs) NaOH -s 31001101 (CBOsNo) (monosodlum starcbats) H10 (ClHsOiNa) CEI! -0 (CsBaOaCHa) (monomsthylstamhste) Nal NH: (CsHsOsCHa) 2Na -s (CsHfOsCl-IiNn) (2-monometbyl. 3,6-disodiuln starcllato) Ha 4.

(CsHfOsCHaNas) 20H11 C|E10i(CHx)| (2,8,trimethyl storchate) 2Nal It is obvious that the non-aqueous sodium hydrnxide reaction is concerned with a position which is not involved in the reaction with metallic sodium and liquid ammonia.

Referring now to the diagrams of the drawings and especially to Fig. 1 for a detailed description of some of the processes oi' our inventions. it may be seen that in the illustrated process, we react starch with an alkali hydroxide in a non-aqueous solvent as is fully described above. The alkali hydroxide may be sodium hydroxide. potassium hydroxide, rubidium hydroxide. caesium hydroxide or lithium hydroxide. Ammonia hydroxide is unsuitable. The nonaqueous solvent may be any solvent other than water which will dissolve sodium hydroxide to the extent oi 0.04N or higher. We have tested and found that the following solvents are all satisfactory and we have found no non-aqueous solvent which is unsatisfactory.

Solvents used It has been found that any oi.' the following alcohols may be used to prepare monosodium starchate provided that certain other variables are sumciently controlled as will be discussed later. It must be understood that not all these mentioned have the same utility in the process. However, any solvent which will dissolve NaOH, even in small amounts, is a suitable vehicle in which to carry out the reaction provided that certain other variables are sufllcientiy controlled.

Alcohols which may be used n Tert. butyl pheuoxy) 5.( o-Methyl cyclohexanoi e h l m-Meth l cyclohexanol Capry p-Methy cyclohexanol Ceryl il-methyl pentanol-l Oetyl Methyl isopropyl carbiuol 3-chloro-2-propenol-1 n-Nonyi Cinnamie n-Octyl Crotyl ctanol-2 Cyclohexanol Phenyl-propyl Der-yl n-Propy Diacetone Iso-propl Dieth l earbinol Tetrnhy rolurfuryi Trlethyi carblnol Dimet yi beniyl earbinol Triphenyl carhinol Dimethyl ethynyl carbinol Dimethyl n-propyl earbinol Various polyhydric alcohols which may also be used methylene glycol monobenyl e er Dlethylene glycol monobutyl et er Di-propyleno glycol Glycerol Glycerol o-n-butyl ether Glycerol auf-dimethyl ether Glycerol a,'ydiphenyl ether Glycerol o-monomethyi ether Hexametbyiene glycol 2-methyl2,4pentanedlol Propyillene glycol Triet ylene glycol Trimethylene glycol Eth iene glycol Ethlene glycol inonomethyl et er Ethylene glycol monoetbyl er Ethylene glycol monobenzyl ether Ethylene glycol monobutyl ether Diethylene glycol Diethylene glycol monomethyi ether Dlcthylene glycol monoethyl ether It is clear thereiore that all non-aqueous solvents capable o! dissolving the alkali to an extent comparable with the dissolving of sodium hydroxxide to the extent ot 0.04 N or higher are satisiactory. Step one oi the process illustrated in Fig. l thus produces a Z-monoalkali starchate having a formula:

As a second step of the process disclosed in Fig. l, we treat the 2monoalkali starchate formed by step 1 above with an etherifying agent. We may suspend the starchate in from 1 to l0 times the calculated quantity of an etheritying agent and heat (with pressure, if desired) to 80-81" C. for from 2 to 24 hours. By this step we obtain a 2-monoorganic starchate having a formula:

A dispersing solvent may be used i! desired but is unnecessary. The reactants may be agitated or not, as desired. Pressure may be applied or not, as desired. The 2-monoalkali starchate may be treated in other manners with the organic compounds il desired. In the drawings, as examples we have designated these reactants as 8 organic halides, but any organic compound containing a replaceable halogen or similarly reacting group ls satisfactory. For instance, dimethyl sulfate, amyl nitrite, nitro parailins, organic phosphates, acetates, benzoates. etc. are satisfactory. As further examples of the reactants which will react with the monoalkali metal or metallic starchate to produce the corresponding 2-monoethers or such carbohydrates, the following may be mentioned:

Acetodichlorohydrin Allyl bromide Allyl chloride Allyl iodide n-Amyl bromide Iso-amy] bromide lso-amyl chloride '.lert.amyl chloride Amylene dichloride Iso-amyl iodide Bemsalacetophenone dibromide Benzal chloride Bensotrichloride Benzyl bromide Benlyl chloride Bromoacetic acid o-Bromoaeeto--naphthone u-Bromo-n-butyric acid 2bromo1chloropropane Bromocyciohexane B-Bromoethyl ether B-Bromoethyi phenyl ether Bromoform 2-bromo-n-octane -Broinophenacyl bromide romopicrin a-Bromopropionic acid -Bromopropionic acid y-Bromopropyl phenyl ether n-n-Valeric acid a-Bromo-iso-valerie acid -Butyl bromide so-butyi bromide Sec-butyl bromide Tert.butyi bromide ,-Dlbromobutyric acid 2,3-dibromopropene n-dibromopropionic acid a,dibromopro lalcohol 3,.-dibromopyr ine ,-Dibromosucclnlc acid Dichloroacetic acid ,'y'-Dichloro ropyl ether BDichloro isopropyl ether hydrin Ethyl bromoacetate Ethyl a-bromo-n-butyrate Ethyl a-bromo-n-caproate Ethyl bromomalonate Ethyl a-bromopropionate Ethyl -bromopropionate Ethyl a-bromo-lsovalerate Ethyl chloride Ethyl chloroacetate Ethyl o-chloroacetoacetate Ethyl chlorocarbonate Ethyl -chloropropionate Ethyl dibromoacetate Ethyl dlbromomalonate Ethyl dichloroacetate Ethylene bromohydrln Ethylene bromide Ethylene chloride Ethylene chlorobromide Ethylene chlorohydrln Ethylidene bromide Ethylidene chloride Ethyl iodide isopropyl bromide n-Propyl chloride Isopro yl chloride Propy ene bromide Propylene bromohydrln Propylene chloride Propylene chlorobromide Propyleue chlorohydrin s-Tetrabromoethane s-Tetrachloroetbane Tetrachloroethylene 1.1,2-tribromoethane Trlbromoethylene 1.2.3-tribromo-2-methyl proune ,3-tribromopropane i 'frichloroacetic acid Trichloro-tert.butyl alcohol and similarly reacting pecially the esters.

n-Butyl chloride lso-butyl chloride See-bn yl chloride Tera-butyl chloride n-Bntyl chloroacetate Iso-but l chlorocarbonate n-Buty ene bromide -Butylene bromide so-but iene bromide n-Buty ideiid chloride Tern-bu yl iodide ietyl bromide Cetyi iodide hloral Chloroacetamide Chloroacetoxlieth iamide Choloroncetic nc d Choloroacetoue Choloroucetonitrile Cblorobutane -Chlorobutyric acid -Chiorobut ronitrile .hiorocyclo exane B-Chloroethyl acetate -Chlomethyl chiorocarbonate chloroform Chloropicrin n-Chloropropionic acid -Chloropropionic acid -Chloropropionitrile ir-Chloropropyl chiorocarbon- Decamethylene bromide Ethyl Trichloroacetate Glycerol ,y-dlbromohydrin Glycerol u, -dichlorohydrin Glycerol a-dichlorohydrin Gl cerol a-monochlorohydrin neptyl bromide n-Heptyl iodide Hexachloroethnne Hexamethylene bromide n-Bexyl bromide n-Hexyl chlorocarbonate n-Hexyl iodide Iodoacetic acid Iodoform Lauryl brolnide Lauryl chloride Methyl bromide Methyl bromoacetate Methyl -bromopropionate Methyl chloroacctate Methyl chlorocarbonato Methyl chloroform Methyl o,dibromopropionnie Methyl u-dlchloropropionnie Methylene bromide Methylene chloride Methylene iodide Myrlstyl bromide Methyl iodide n-Nonyl bromide n-Octadecyl bromide n-Octadecyl chloride lhenacyl bromide Phenacyi chloride n-Propyl bromide 2.2,3trichlorobutyric acid 1,1,2-trichloroethnne 'lrichloroethylene 1.2.3-trichloro ropane Triglycol dich oride Trimethylene bromide Trimethylene bromohydrln Trlmethylene chloride Trimethylene chlorobromide Trlmethylene chlorohydrin Triphen lchloromethnne o-Xylyl romide m-Xylyl bromide p-Xylyl bromide o-Xylylene bromide o-Xylyicne chloride chemicals including es- The starchate may be dispersed with the organic compound in any suitable solvent. In addition to the solvents mentioned above, as solvents for the sodium hydroxides the following dispersing solvents may also be used:

Bec.smyl henlene n-Octane Tern-amy] benlene Iso-octane nsene n-Pentsne n-Butyl bensene Petroleum ether Bec. l o Propyl henlene Tart-butyl bensene Tetrailobutyleno Cumene Tetradecane C clohexano Toluene 2 -dimethyl octane Tri-isobutyleae thyl cyclohexane Trlmethyl betsne Hcptane Trimethyletbylene Hexano 2 2,4-trimethyl pentane Hexadeeane 'fri henyl methane Llgroin oiene Methyl cyclohexane mylene Nonane p-Xylene and various others.

The following ketones may also be used:

Acetone Methyl nmyl Aceto benone Methl butyl Aniso acetone o-Me yl cyclohexanone Bensslacetone m-Mcthyl cyclohexnnone Bensophenone Metbyl cyclohexanone Bennoylacetone ethyl ethyl Diethyl Methyl hexyl diiso ropyl Methyl n-propyl llithyil phenyl Methyl isopropyl Ethyl undecyl and various others.

The following ethers may also be used:

Allyl Bensyl ethyl Ally] ethyl Chloromethyl n-Amyl Dichloromethyl Iso-amyl Di'ethylene glycol diethyl Anethole Hit hyl bu l Anlsole Ethylene glycol dibens'l Benzyl Et bylene glycol diethy Bensylmethyl Ethyl n-Butyl benzyl Phenetole n-Butyl n-Hexyl n-Butyl phenyl n-Propyl 1,4-dioxane Iso-propyi Di-n-propyl and various others.

By these various lists we do not mean to exclude the any other dispersing solvents.

As step three of the process shown in Fig. l, we react 2-monoorganic starchate resulting from step two with an alkali hydroxide in a non-aqueous solvent in the same manner as in step one with the difference that the temperature is raised to 115 C. or higher and provision is made for the removal of water. The same solvents as areusedinsteponsaresuitable; thesamealkali hydroxides are suitable. The alkaline reacting material should have an ionization constant or 2x10-s or greater in a solvent containing enough of the alkali in solution to produce 0.04 N or higher at a temperature of 115' C. There may be agitation or not as desired. The reaction should continue for a period of one hour or longer. There must however be a provision for removal ci' water formed in the reaction. This is most important and the provision for the removal o! water tosether with the higher temperature distinguish this step from the requirements ot step one. It n essential as stated that the water evolved in the reaction be removed as rapidly as formed and therefore only those alcohols boiling at 115" C. or more have any utility as solvents in the reaction except in special cases where some other means have been devised to remove the water. At 115 C. the water is removed by boiling or distillation. At temperatures below 115 C. special means must be provided for removing the water. This step of the process produces a 2mono organic, B-monoalkali starchate, having a tormula of The fourth step or the illustrative process is similar to the second step. It comprises the reaction ci the product of the third step with an organic reactant. This may be the same orsanic reactant as used in connection with the second step, or it may be a different organic reactsnt. It may be any one of the organic halides or similar reactants mentioned above in connection with step two. 0n treatment of the product. there is a reaction to produce a 2,3-diorganic starchate having a formula of l c /H nooni-unamH-)-(onoRI|)-(onoal)o In this step, as in the preceding step. the temperature should be kept at C. or higher and precautions should be taken to prevent water contamination.

The ith step of the illustrative process comprises the reaction of the product of the fourth step with an alkali metal dissolved in ammonia. As pointed out above, this process which comprises the iiith step is a step known in the prior art. However. we combine it with the previous steps of thisprocess and the combination becomes a new process because it involves a new combination of steps, some of which are old and some oi which are new. Moreover, an entirely new product is obtained by this reaction. By it, we produce a 2.3-diorganic, 6-monoalka1i starchate having a formula ot The seventh step of the illustrative process comprises the treatment of the 2,3,6-triorganic starchate produced in the sixth step with an alcoholic acid solution to obtain a 2.3,6-triorgenie. s-alkyl glucoside having a formula of nul-ocin-lgH(cnom-wnonlo-(onoRn-J:noa" This glucosidic hydrolysis of the starchate is somewhat similar to the giucosidlc hydrolysis or f starch according to the prior art. However, we combine this step with the preceding new and old steps o! our process into a new combination of steps. By this entirely new combination procoss we produce entirely new products.

The eighth step illustrated comprises an etheriiication of the product of the seventh step to produce a 2,3,4,6tetraorganic, a-alkyl giuoside having a formula ot Aprocessanalogoustoanyoneofseveralot the prior art processes may be used in this step in combination with our other new and old steps. l'br instance. prior to our invention starch has been methylated (l) by the use of methyl iodide and silver oxide, (2) by the use of di-methyl sul- Pilate and sodium hydroxide, (3) by the use of etherify the carbon atoms processes disclosed in Fis. 2 are different from the order ci the steps disclosed in Fig. l, so that some new and different products are obtained. The processes disclosed in Figs. 3 and 5 and the products of such processes are the inventions particularly covered by this application.

In the processes disclosed in Fig. 3 the ilrst step diners from the first step of the processes disclosed in Figs. 1 and 2. Although certain of the same end products may be produced either by the main process disclosed in Fig. 3 or by the main processes disclosed in Figs. 1 and 2, the processes themselves are different, some intermediate products are different and some alternative processes produce some ditlerent products. The processes of Figure 3 by reason of the change in the initial step are obviously dierent from the processes described in connection with Figs. 1 and 2. In the main process disclosed in Fig. 3 starch is reacted with an alkali metal dissolved in ammonia to produce a B-monoalkali starchate having a formula of This B-monoalkali starchate is then reacted as previously described with an organic reactant to produce a -monoorganic starchate having a formula of /H Rl-ocardu-(cH-)(cHoH)-(cnon)co It may be noted that this -monoorganic starchate differs from the 2-monoorganic starchates produced by the processes disclosed in Figs. 1 and 2. This -monoorganic starchate is subsequently reacted with an alkali hydroxide in a non-aqueous solvent in the manner previously described in connection with the reaction of starch in step one of the processes previously described. This reaction produces a -monoorganlc, 2-monoalkali starchate having a formula n n1ocm-n-(cHs-(cnouq-(cHoare-fo- By reaction with an organic reactant as in the 12 processes previously described a 2.3,6-triorganic starchate may be produced having a formula of c n BL-ooHr-H llz/ -(CH-)-(CHORm)-(CHORU) -o- This 2.3,6-triorganic starchate may be reacted by glucosidic hydrolysis, acid hydrolysis, esteriflcation, etherication, condensation. degradation, oxidation, reductions and so forth.

The B-monoorganic starchate and the 2,6-diorganic starchate may also be reacted by glucosidic hydrolysis, acid hydrolysis, etheriilcation. esterification, condensation, degradation. oxidation, reduction and so forth to produce other compounds not previously mentioned. The -monoalkali starchate; the G-monoorganic, 2- monoalkali starchate; and the 2.6-dicrganic, 3- monoalkali starchates may be reacted with' a metallic salt to produce corresponding monometallic starchates which may be further reacted by the replacement of the anion groups of multiple valent derivatives.

The processes disclosed in Fig. 4 are similar in many respects to those disclosed in the nrst portion o1' Fig. l.

However, alternative processes disclosed in Fig. 4 are different from any of the processes previously disclosed in connection with Figs. l, 2 and 3. Thus we show that the 2-monoalkali starchate may be reacted with a metal salt to produce a 2-monometallic starchate having a formula of H HOCEngli-(CH-) (CHOID-(CHOLD-o- The 2-monoorganic, 3-monoalkali starchate may be reacted with a metallic salt to produce a 2-monoorganic. 3-metallic starchate having a formula of c /n Hocm-JJH-(crr)-(cnoM)-(cnoRI)-J:o- The` 2,3-diorganic 6-monoalkali starchate may be reacted with a metallic salt to produce a 2,3-

diorganic 6-metallic starchate having a, formula of These glucosides may be then further reacted by etherlflcation and so forth. 0r the 6-monoorganic starchates may be reacted with water and acid to eilect acid hydrolysis of the starchates to produce 6-monoorganic glucoses having tormulas ot sL-ocmn-(cnom-(cHom-(cnomnon These glucoses may be fin-ther reacted by etheriiication. condensation, degradation and so forth. Moreover, the 6-monoalkali starchates may be 'mess e-monometams stai-chates may be further modified by the replacement of anion groupe of multiple valent derivatives.

Above in connection with Figures 2. 3. 4 and 5 we have described the replacement of alkali metals with non-alkali metals by reaction of the alkali starchates with metal salts. In each of the cases specified we can, if we wish. use a non-metal inorganic salt as the reactant instead oi a metal salt and obtain instead of the nonalkali metal starchates described in connection with said Figures 2. 3, 4 and 5 corresponding non-metal inorganic starchates. Thus in fact we can react the alkali metal starchates with any salt, organic or inorganic. metal or nonmetal and obtain corresponding organic or inorganic. metal or non-metal starchates.

From the above it will be clear that it is impossible to give examples of the synthesizing of all of the products possible by our improved process or even to give examples of all of the hundreds of products which we have actually synthesized.

Following are examples of the synthesis of various products by the use of processes of our invention.

Inasmuch as certain steps of the procedures involved in many of the examples were identical or substantially identical, we set out now a series of directions or procedures which are followed in performing such steps. These directions or procedures are designated as Procedures l-13, inclusive and in each oi' the examples. we have merely stated that certain of these procedures were employed. Thereby we have not only reduced the work of writing out the examples but have also, we believe, presented the examples in a manner by which they may be more readily understood. Following are the thirteen procedures referred to.

PROCEDURE 1 Preparation of z-sodium starchate In a 1000 mi. three-necked ask fitted with an emcient agitator and a thermometer place the following:

100 grams of starch 22 grams of sodium hydroxide 500 ml. butanol Heat this mixture to 85 C. for 2 hours with vigorous agitation. Filter on suction, wash with butanol and then with toluene. 'I'he product. at this stage can be used directly in Procedure 4. The product may, however, be dried to produce 2-sodium starchate. The 2sodium starchate must be protected from moisture and carbon dioxide during filtration, processing and drying. Drying can be best effected in a vacuum at temperatures below 100 C.

PROCEDURE 2 Preparation of 2,3-disodium starchatc (or 3-sodium starchdte if C-Z is occuplied by an organic radical) In a 1000 m1. Claissen sk tted with Bn 14 ei'iicient agitator and a thermometer place the following:

grams of starch 40 grams of sodium hydroxide l ml. butanol Slowly distil with vigorous agitation until the distillation temperature ceases to rise (ox-'when the temperature reaches 118 CJ. Filter hot with elaborate precautions to avoid contamination by moisture and wash twice withanhydrous butanol then with anhydrous toluene.

The product, at this stage, can be used directly in Procedure 4. 'Ihe dry product is unstable.

If C-2 is occupied by R then the amount of sodium hydroxide should be cut to 20 grams.

PROCEDURE 3 Preparation of 6sodium starchate (or on any free hydroxyl group with the exception of nafive starch in which case it is only on C6) In a 1000 ml. three-necked flask fitted with an efficient agitator, an ammonia inlet and a stopper, and immersed 2 inches in a Dry Iceacetone bath, place the following:

Pass dry ammonia gas into the flask until 500 mi. of liquid ammonia have been condensed. Introduce 25 grams of dry starch which soon disperses in the liquid ammonia under the influence of agitation. Add sodium wire piece-wise until the mixture turns blue (3.5 to 3.7 grams). The excess sodium, indicated by the blue color. may be destroyed by small amounts of carbon dioxide.

The ammonia is removed by evaporation and the product may be used directly in Procedure 4.

PROCEDURE 4 Etheriflcation according to the reaction RONa+R1X ROR1+NaX 'I'he sodium starchate prepared according to Procedure 1, 2 or 3 is suspended in anhydrous toluene according to the following:

100 grams of starch (converted into the sodium starchate) 200 ml. toluene 100 ml. of the organic halide PROCEDURE 5 Glacosidic hydrolysis rn a zooo m1. three-neeld naar sited with an eillcient agitator, a thermometer and a reilux condenser. place the following:

1500 ml. anhydrous alcohol (according to the glucoside desired) Pass in dry HC1 gas until the solution becomes 0.5% HC1 and then add 100 grams starch (converted into the starch ether) Reflux with agitation until the optical rotation becomes constant (48 hours). The acidity of the solution should be checked periodically so that an acidity of 0.25 to 0.50% may be maintained. At the completion of the hydrolysis the solution is concentrated to about 800 inl. under vacuum. Any unetherined glucose will crystallise as an s-alkyl glucoside (e. g. s-methyl glucoside it methyl alcohol was used). from this solution on cooling and can bs removed by illtra- PROCEDURE Acid hydrolysis In a 2000 ml. three-necked flask iltted with an eillcient agitator, a thermometer and a reflux condenser place the following:

100 grams oi starch (converted into the starch ether) 1500 mi. 0.5% HC1 solution Redux with agitation until the optical rotation becomes constant (4B to '12 hours).

At the completion oi the hydrolysis. add 50 grams of silver oxide and the solution is concentrated under. vacuum to a volume of 500 ml.

and then illtered hot through a iilter aid and decolorizing carbon.

The solution is then evaporated to a sirup and taken up in alcohol whereon the polyamyloses ars precipitated. 'Ihe alcohol solution is then evaporated and the substituted glucoses are crysstallized or separated in the usual manner.

PROCEDURE I Etherificotion according to the reaction ROH-l-RX-l-NaOH-RORI-l-NaX-i-Hzo In a 100 m1. three-necked flask tted with an emcient agitator, a thermometer and a reilux condenser. place the following:

100 grams oi' starch (converted into the derivative) 750 ml. 20% sodium hydroxide 100 ml. organic halide Heat this mixture at 95 to 105 C. for iour hours with vigorous agitation. Neutraliae the reaction mixture with HC1 (1:1) and concentrate to a sirup under a vacuum. Take up the ether in alcohol and purify in the usual manner.

PROCEDURE B Wohl's degradation (Cohen. part III, 4th ed.,

PROCEDURE 9 Acefyldtion In a 750 ml. Erlcnmeyer ntted with a nnger condenser place the following:

10 grams of starch (converted into the derivative) 300 ml. acetic anhydride 30 grams fused sodium acetate Heat this mixture lust below the boiling point for about i hours. The unreacted acetic anhydride and acetic acid formed is removed by vacuum distillation, care being taken as the mixture approaches dryness.

The reaction product is removed by extraction with appropriate solvent, recovered and puriiled in the usual manner. Y

PROCEDURE 10 Dco'lucosidation The glucoside radical may be easily removed by the standard procedure consisting essentially of allowing the glucoside to stand at room temperature with 1 N aqueous hydrochloric acid and the tree aldose may be separated in the usual manner.

PROCEDURE 1l Oxidation The glucose derivative corresponding to grams of starch is dissolved in 1000 ml. 10% sul- Iuri'c acid. This mixture is placed in a 2000 ml. three-necked ask immersed in ice water. with eihcient agitation 100 grams potassium permanganate is added in 5 gram portions. At no time is the temperature allowed to rise over 20 C. At the end oi' the reaction period (about 2 hours) the excess KMnOil is destroyed by a stream of sulfur dioxide. The acid solution is neutralized with barium carbonate and the solution evaporated to dryness. The barium salt of the gluconic acid is extracted with alcohol and the product ilnished in the usual manner.

PROCEDURE 12 Reduction The glucose derivative obtained from 100 grams o! starch is dissolved in 1000 mi. of i0 N methanolic KOH at 60 C. 400 m1. formalin is then added and methanol added at such a rate that the temperature remains between 60 and '70 C. When the temperature drops the mixture is heated, with agitation, and the temperature maintained at this point i'or 3 hours and then cooled.

The alkali is neutralized with sulfuric acid (1 5) and the mixture evaporated under vacuum to a sirup. The product is extracted with alcohol and puried in the usual manner.

PROCEDURE 13 Preparation of phenylhydrazones The glucose derivative is converted into the phenylhydraaone by dissolving in acetic acid and then treating with phenylhydraaine base in the usual manner. Prolonged heating is to be avoided.

The crystalline hydrazone is purified by recrystallization from dilute alcohol in the usual manner.

The procedures set out in detail above (with exception oi those listed as Procedures l. 2 and 3) may be modified within wide limits without endangering the expected result.

17 Procedure i may be modiil'ed as described in copending applications but the procedure given istheonewer'eeommendioruseinconiunction with the other procedures referred to.

Procedure2maynotbemodiiiedinanyway other than relative to the alcohol used. The mixture must boil at temperatures of 113 to 135 C. Other defined conditions are required.

Procedure 3 may be modied somewhat as the requirements dictate but the procedure described has been found to be generally most satisfactory.

Example L Spnthesis of iii-ethyl, 3n propel, 6-n butyl-s-methvl-D-elacoside The following enumerated steps are used to prepare this glucoside.

1. Procedure 1 applied to produce 2sodium starchate.

2. Procedure 4 applied with ethyl bromide to produce 2ethyl starchate.

3. Procedure 2 applied to produce 2-ethyl. 3- sodium stsrchate.

4. Procedure 4 applied with n-propyl bromide to produce 2-ethyi, 3-n propyl starchate.

5. Procedure 3 applied to produce -ii-ethyl. 3-n, propyl. il-sodium starchate.

6. Procedure 4 applied with n-butyl bromide to produce 2-ethyi, 3-n propyl. ii-n butyl starchate.

'1. Procedure 5 applied with methanol to produce 2-ethyl. 3-n propyl. 6n butyl. a-methyl-D- Ulucoside..

Example Il. Synthesis of 2-n butyl. 3-n propyl, -ethpl, a-methyl-D-plucoside The following enumerated steps are used to prepare this glucoside by a method consisting of a combination of steps differing from or differing in order from the steps of the method described in Example I.

l. Procedure 3 applied to produce il-sodium starchate.

2. Procedure 4 applied with ethyl bromide to produce 6cthyl starchate.

3. Procedure 1 applied to produce 2-sodium, G-ethyl starchate.

4. Procedure 4 applied `with n-butyl bromide to produce 2n butyl, 6ethyl starchate.

5. Procedure 2 applied to produce 2-n butyl. 3- sodium. 6ethyl starchate.

8. Procedure 4 applied with n-propyl bromide to produce 2n butyl, 3n propyl. 6-ethyl starchate.

7. Procedure 5 applied with methanol to produce 2-n butyl, 3-n propyl, -ethyl. methyl-D- glucoside.

Example IIL-Synthesis of Z-ethyl, .l-beneyl.

6is0pr0iwl a-methyl-D-nlucoside The following enumerated steps are used to prepare this glucoside by a method consisting of a combination of steps diifering from or diiiering in order from the steps oi the method described in Examples 1 and 2. l

i. Procedure 3 applied to produce 6sodi starchate.

2. Procedure 4 applied with isopropyl bromide to produce 8lsoilr0i 7l starchate.

3. Procedure 1 applied to produce 2sodium. isopropyl starchste.

4. Procedure 4 applied with ethyl bromide to produce 2ethyl. 6-isopropyl starchate.

5. Procedure l applied4 with benzyl chloride to produce 2ethyl, 3-benzyi. 6-isopropyl starchate.

6. Procedure 5 applied with methanol to pro- 18 duce-2-ethyl. S-bensyl. B-isopropyl. methyl-D- slucoside.

Example IVF-Synthesis of 2-n propul, .i-isoproppl, d-benzpl-.D-alucose The following enumerated steps are used to prepare this glucose derivative.

i. Procedure l applied to produce S-sodium starchate.

2. Procedure 4 applied with n-propyl bromide to produce 2-n propyl starchater 3. Procedure 2 applied to produce 2-n propyl, 8sodium stai-chate.

4. Procedure 4 applied with isopropyl bromide to produce 2-n propyl, 3-isopropyl starchate.

5. Procedure l applied with benzyl chloride to produce 2-n-propyl, 3-isopropyl, -benzyl starchate.

6. Procedure 6 applied to produce 2-n propyl. 3isopropyl, il-benzyl-D-slucose.

Enample tif-Synthesis of 2methyl. .li-isopropyl. d-n-proppl-D-alucoss The following enumerated steps are used to prepare this glucose derivative by a method consisting of a combination of steps diilering from or diiiering in order from the steps of the method described in Example 4.

1. Procedure 3 applied to produce S-sodium starchate.

2. Procedure 4 applied with n-propyl bromide to produce 6-n propyl starchate.

3. Procedure l applied to produce n-sodium, d-n propyl starchate.

4. Procedure 4 applied with methyl iodide to produce 2-methyl, 6-n propyl starchate.

5. Procedure 2 applied to produce 2methyl, 3sodium. il-n propyl starchate.

6. Procedure 4 applied with isopropyl bromide to produce 2-methyl, 3-isopropyl, B-n propyl starchate.

'7. Procedure 6 applied to produce 2inethyl, 3isopropyl, 6-n-propyl-D-glucose.

Example vL-Sunthesis of Z-n propri. J-methpl. 6-isobutyl-D-plucose I'hc following enumerated steps are used to prepare this glucose derivative by a method consisting of a combination oi' steps difiering from or differing in order from the steps of the method described in Examples 4 and 5.

1. Procedure 1 applied to produce 2-sodium starchate.

2. Procedure 4 applied with n-propyl bromide to produce 2-n propyl bromide.

3. Procedure 2 applied to produce 2n propyl, 3sodium starchate.

4. Procedure 4 applied with methyl iodide to produce 2-n propyl, 3methyl starchate.

5. Procedure 3 applied to produce 2n propyl, 3-methyl, 6-sodium starchate.

6. Procedure 4 applied with isobutyl bromide to produce 2n propyl, 3methyl, B-isobutyl starohate.

7. Procedure 6 applied to produce 2n propyl, 3-methyl, 6-isobutyl-D-glucose.

Example VIL-Synthesis of 2-monomethpi-amethyl-D-glucoside The following enumerated steps are used to prepare this glucoside.

1. Procedure i applied to produce 2-sodium starchate.

2. Procedure 4 applied with methyl iodide toproduce 2-methyl starchate.

19 3. Procedure applied with methanol to produce 2-methyl-a-methyl-D-glucoside.

Example WIL-Synthesis of 6-monomethpl-amethyl-D-alucoside The following enumerated steps are used to prepare this glucoside.

1. Procedure 3 applied to produce 5-sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 6-methyl starchate.

3. Procedure 5 applied with methanol to produce 6-methyl-a-methyl-D-glucoside.

Example IX.-Synthesis of 2methul, l-ethyl-an propyl-D-alucosde The following enumerated steps are used to prepare this glucoside.

l. Procedure 3 applied to produce 6sodium starchate.

2. Procedure 4 applied with ethyl bromide to produce ii-ethyl starchate.

3. Procedure 1 applied to produce 2-sodium. 6-ethyl starchate.

4. Procedure 4 applied with methyl iodide to produce 2methyl, d-ethyl starchate.

5. Procedure 5 applied with n-propanol 'to produce 2-methyl, B-ethyl-a-n propyl-D-glucoside.

The following enumerated steps are used to prepare this glucoside.

1. Procedure 1 applied to produce 2sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 2methyl starci-nate.

3. Procedure 2 applied to produce 2methyl, 3-sodium starchate.

4. Procedure 4 applied with ethyl bromide to produce 2methyl, 3-ethyl starchate.

5. Procedure 5 applied with n-propanol to produce '2i-methyl, 3ethylan propyl-D-glucoside.

Example JEL-Synthesis of 2-methul, 3-beazyl, 6-n propyl-a-phenyl-D-clucoside The following enumerated steps are used to prepare this glucoside.

1. Procedure 3 applied to produce 6-sodium starchate.

2. Procedure 4 applied with n propyl bromide to produce 6-n propyl starchate.

3. Procedure l applied to produce 2-sodium, 6n propyl starchate.

4. Procedure 4 applied with methyl iodide to produce Z-methyl, 6-n propyl starchate.

5. Procedure 'l applied with benzyl chloride to produce 2-methyl, 3benzyl, 6n propyl starchate.

6. Procedure 5 applied with phenol to produce 2-methyl, 3benzyl, 6n propyl-a-phenyl-D-glucoside.

Example JUL-Synthesis o! 2-ethyl. 3-methyl. 6-isopropyl-a-benzyl-D-glucoslde The following enumerated steps are used to prepare this glucoside.

1. Procedure 1 applied to produce 2-sodium starchate.

2. Procedure 4 applied with ethyl bromide to Y produce 2-ethyl starchate.

3. Procedure 2 applied to produce 2ethyl. 3- sodium starchate.

4. Procedure 4 applied with methyl iodide to produce Z-ethyl, 3-methyl starchate.

5. Procedure 3 applied to produce 2ethyl.'3 methyl, -sodium starchate.

6. Procedure 4 applied with isopropyl bromide to produce 2-ethyl, 3-methyl. 6isopropyl starchate.

7. Procedure 5 applied with benzyl alcohol to produce 2-ethyl. 3methyl, -isopropyl-n-benzyliii-glucoside.

Example XUL-Synthesis of 2-metlwl-D- glucose 'Ihe following enumerated steps are used to prepare this glucose derivative.

1. Procedure 1 applied to produce 2-sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 2-methyl starchate.

3. Procedure 6 applied to produce 2-methyl- D-glucose.

Example JUIL-Synthesis of G-methul-D-nlucose The following enumerated steps are used to prepare this glucose derivative.

1. Procedure 3 applied to produce 6sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 6methyl stal-chate.

3. Procedure 6 applied to produce 6methylD glucose.

Example XV .-Sunthesis of 2,3-dimethyl-D- glucose The following enumerated steps are used to prepare this glucose derivative.

l. Procedure 2 applied to produce 2.3-disodium starchate.

2. Procedure 4 applied with methyl iodide to produce 2.3-dimethyl starchate.

3. Procedure 6 applied to produce :a-dimethyl. D-glucose.

Example XVI.-Svnthesis o! 2,6-dlmethul-D glucose The following enumerated steps may be used to prepare this glucose derivative.

1. Procedure 3 applied to prepare -sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 5-methyl starchate.

3. Procedure l applied to prepare 2-sodium, 6methyl starchate. i 4. Procedure 4 applied with methyl iodide to prepare 2,6-dimethyl starchate.

5. Procedure 6 applied to produce 2.6-dimethyl- D-giucose.

2l produce 2-methyl. B-etbyl, t-butyl, 8bensylmethyl-D-glucoside.

Izmple :WHL-Synthesis of ti-methyl, .l-ethyl. (-butyl, 6-beazyi-n-methyl-D-oiuooside The following enumerated steps are used to prepare this glucoside.

l. Procedure 3 applied to produce B-sodium starchate.

2. Procedure 4 applied with benzyl chloride to produce d-benxyl starchate.

3. Procedure i applied to produce 2-sodium, 6- bensyl starchate.

4.Procedure4appliedwithmethyliodideto produce 2methyl. -bcnayl starchate.

5. Procedure 2 applied to produce 2methyl, 3-sodium. 6-bemsyl te.

d. Procedure 4 a with ethyl bromide to produce 2-methyl. Bhethyl. ii-beuzyl starchate.

'7. Procedure /applied with methanol to produce 2-methyl -ethyl. 6-benzyl, methyl-D- slucoside.

l. Procedure '1 applied with butyl bromide to produce 2-methyl. ii-ethyl, 4butyl, B-benzyl-amethyl-D-glucoside.

The following enumerated steps are used to prepare this glucoside.

i. Procedure l applied to produce 2sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 2-methyl starchate.

3. Procedure 2 applied to produce til-methyl, 3-sodium starchate.

4. Procedure 4 applied with ethyl bromide to produce 2-methyl. -ethyl starchate.

5. Procedure 3 applied to mi* 2-methyi, -ethyl. ii-sodium starchate.

6. Procedure 4 applied with benzyl bromide to produce 2methyl. 3-ethyl, 8benzyl starchate.

'L Procedure 5 applied with methanol to produce 2-methyl, 3-ethyl, 6-bensyl methyl-D- glucoside.

B. Procedure 7 applied with butyl bromide to produce il-methyl. ii-ethyi, 4-butyi. B-benzyl-amethyl-D-glucoside.

The following enumerated steps are used to prepare this glucose derivative.

1. Procedure 1 applied to produce 2-eodium starchate.

2. Procedure 4 applied with methyl iodide to produce 2-methyl starchate.

3. Procedure 2 applied to produce 2methyl. 3-sodium starchate.

4. Procedure 4 applied with ethyl bromide to produce 2-methyl. 3-ethyl starchate.

5. Procedure 'I'applied with n-butyl bromide to produce 2methyl. 3ethyl. dai-butyl starchste.

6. Procedure 8 applied to produce 2-methyl, 3-ethyl 6-n butyl-D-glucose.

7. Procedure 9 applied with acetic anhydride to produce 2-methyl. 3-ethyl, 4,5-diaceto. B-butyl- D-glucose.

The following enumerated steps are used to prepare this glucose derivative.

l. Procedure 1 applied to produce 2sodium starchate.

Ill)

2. Procedure 4 applied with methyl iodide to produce 2methyl stai-chate.

3. Procedure 2 applied to produce 2-methyl, 3sodium starchate.

4.Procedure4appliedwithethylbromideto produce 2-methyl. 3-ethyl starchate.

5. Procedure 3 applied to produce 2-methy. il-ethyl. 6sodium starchate.

8. Procedure 4 applied with n-butyl bromide to produce 2-methyl, 3-ethyl, 8-u-butyl starchate.

'1. Procedure 6 applied to produce 2-methyl. 3-ethyl, 6n-butyl-D-glucose.

8. Procedure 9 applied with acetic anhydride to produce 2-methyl. 3-ethyl. 4,5-diaceto. 6n butyl-D-sluccse.

Example XXXL-Synthesis of 2-methyl, .l-ethpl, 4,5-diacetyi. -butyI-D-plucose The following enumerated steps are used to prepare this glucose derivative.

i. Procedure 3 applied to produce 6-eodium starchate.

2. Procedure 4 applied with butyl bromide to produce 6nbutyl starchate.

3. Procedure i applied to produce 2-sodlum. d-n butyl starchate.

4. Procedure 4 applied with methyl iodide to produce 2-methyl. 6-n butyl starchate.

5. Procedure 2 applied to produce 2-methyl. 3sodium. 8-n butyl starchate.

6. Procedure 4 applied with ethyl bromide to produce 2-methyl. methyl. e-n butyl starchate.

'1. Procedure 6 applied to produce 2methyl. 3ethyl. e-n butyl-D-glucose.

8.Procedure9appliedwithaceticanhydrlde to produce 2-methyl. 3-ethyl. 4,5-diaoeto. 6-n butyl-D-glucose.

Example LWR-Synthesis of Z-etlwl. 3isopropyl. 5-butyl, a-methyI-D-riboside I'he following enumerated steps are used to prepare this glucoside.

l. Procedure 3 applied to produce 6sodium starchate.

2. Procedure 4 applied with n-butyl bromide to produce -n butyl starchate.

3. Procedure i applied to produce 2-sodium. 6-n butyl starchate.

4. Procedure 4 applied with methyl iodide to produce 2methyl, 6n butyl starchate.

5. Procedure 2 applied to produce 2mcthyl. 3sodium. B-n butyl starchate.

6. Procedure 4 applied with ethyl bromide to produce 2methyl. S-cthyl. ii-n butyl starchate.

7. Procedure 6 applied to produce 2-methyl. '8- ethyl. 6-n butyl-D-glucose.

L Procedure 8 applied to produce 2ethyl. ii-u butyl. s-methyl-D-riboside.

9. Procedure 7 applied with isopropyl bromide to produce 2-ethyl. 3-tsopropyl, 5-n butyl, amethyl-D-rlboside.

Example XXIVP-Synthesis of z-methyl, 3-ethyl,

d-loprOWl, 5-acetpl, ammini. D-alucose pheniilwdfdzone The following enumerated steps are used to prepare this glucose derivative.

l. Procedure 1 applied to produce 2-sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 2-methyl starchate.

3. Procedure 2 applied to produce 2-methy1. 3- sodium starchate.

4. Procedure4appliedwithethyliodidetoproduce 2methyl. a-ethyl starchate.

Example xxl-Synthesis of 2-monomethul. 3.4.5.6-nlucose tetraacetate The following enumerated steps are used to prepare this glucose derivative.

1. Procedure 1 applied to produce 2-sodium starchate.

2. Procedure 4 applied with methyl iodide to produce Z-methyl starchate.

3. Procedure 6 applied to produce 2-methyl- D-glucose.

4. Procedure 9 applied to produce 2-methyl, 3.4.5,8-D-glucose tetraacetate.

Example XUL-Synthesis of 2-methyl, 6-ethvl gluconic scid The following enumerated steps are used to prepare this glucose derivative.

i. Procedure sapplied to produce G-sodium starchate.

2. Procedure 4 applied with ethyl bromide to produce 6-ethyl starchate.

3. Procedure l applied to produce 2-sodium, 6-

ethyl starchate.

4. Procedure 4 applied with methyl iodide to produce 2-methyll 6-ethyl starchate.

5. Procedure 6 applied to produce 2-methyl, 6- ethyl-D-glucose.

6. Procedure il applied to produce 2methyl, 6ethylgluconic acid.

The following enumerated steps are used to prepare this glucose derivative.

l. Procedure i applied to produce 2-sodium starchate.

2. Procedure 4 applied with methyl iodide to produce 2methyl starchate.

3. Procedure 2 applied to produce 2methyl. 3- sodium starchate.

4. Procedure 4 applied with ethyl bromide tc produce 2methyl. 3ethyl starchate.

5. Procedure 'I applied with isopropyl bromide to produce 2methyl. 3-ethyl, 6-isopropyi starchate.

8. Procedure 6 applied to produce 2methyl, 3- ethyl. 6-isopropyl-D-glucose.

7. Procedure 12 applied to produce 2-methyl. a-ethyl. -isopropyl sorbitol.

The glucoses and glucosides produced as described above may be esteritled, acetylated, sulionated or subjected to any reaction which an alcohol group will undergo.

1i an organic starchate having an organic group on the C-2 carbon or on the C-6 carbon is (instead of being subjected to glucoeidic hydrolysis or acid hydrolysis) subjected to the action ofv vsrious'amylolytic enzymes as described in the prior art literature, only liquefaction occurs. The reducing value o! the digest does not increase above that which would be expected from the unreacted glucose units. Thus it appears that no hydrolysis of the monoorganic radical takes place. Therefore there is produced a depolymerlzed non reducing soluble starch-like product which may be dehydrated according to the art to produce soluble starch-like products which are readily dispersible in cold water. These products are apparently very hygroscopic and very adhesive.

As stated above, inventions relating to: monometallic starchates (both alkali and non-alkali) monoorganic starchates; polyalkali starchates; polymetallic starchates (non-alkali): polyorganic starchates; and methods for the preparation of all such starchates have or will be fully clisclosed and claimed in co-pending applications. Mono and poly organic non-metallic starchates, the reaction products of starch with sodium hydro-sulilde (NaSH) and sodium sulfide (Naas) and methods for their preparation; starch products which have been depolymerized by amyiolytic enzymes (as are brieiiy described in the last paragraph) and methods i'or their preparation will also be fully disclosed and claimed in copending applications.

It is to be understood that the described embodiments of our invention are only illustrative and are not intended to limit the invention. The scope o! the invention is dened by the following claims.

We claim:

1. A process oi producing substantially uniiormly substituted 2-alkali metaLB-alkyl glucopyranose polymer which comprises the steps oi' reacting starch by mixing it with an alkali metal dissolved in liquid ammonia; mixing the 6-alkali metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to produce a -alkyl starchate; mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range of approximately 80 C. to 115 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a. temperature above '78 C. at 760 mm. pressure with the alkali hydroxide supplied in at least stoichiometric quantities to cause a reaction to produce the 2alkali metal, 6-alkyl starchate.

3. The process o! producing a substantially uniformly substituted 2,6-dialky1 starchate which comprises the steps of reacting starch by mixing it with an alkali metal dissolved in liquid ammonia; mixing the -alkali metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range oi' 80 C. to about 118 C. to produce a 6alkyl starchate; mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range ot approximately 80 C. to 115 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above 78 C. at 760 mm. pressure with the alkali metal hydroxide supplied in at least stochiometric quantities to cause a reaction to produce a 2- alkalL-alkyl starchate; and reacting the 2al kalm-alkyl starchate by mixing it with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to produce the 2,6-dialkyl starchate.

3. A process oi preparing a substantially uniformly substituted starch derivative comprising in combination thesteps ci substituting un Blkalimetalatominplaceofthehydrogen atom ci the hydroxyl group oi each oi a plurality oi.' the various units comprising the starch molecule by mixing starch with an alkali metal diolved in liquid ammonia to i'orm a 8alkall metal starchate; mixing the 8-alkall metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to produce a 8-alkyl starchate; mixing the alkyl starcliate so formed with an alkali metal hydroxide at a temperature in the range o1 approximately 80 C. to 115 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above '18 C. at '180 mm. pressure with the alkali hydroxide supplied in atleast stoichiometric quantities to cause a reaction to produce a monoanzyl-monoalkali metal starchate: reacting the monoalkyl-monoalkali metal starchate so formed by mixing it with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 88 C. to about 118 C. to form a polyalkyl starchate therefrom in which the substituted alkyl groups on at least two oi' the carbon atoms are different: and mixing the polyalkyl starchate so formed with an alkali metal hydroxide at a temperature in the range oi approximately 115 C. to 118 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above 78 C. at 760 mm. pressure with the alkali hydroxide supplied in at least stoichiometric quantities to cause a reaction to produce a polyalkyl monoalkali metal starchate.

4. A process of producing a substantially uniformly substituted mixed metal alkyl starchate which comprises the steps of reacting starch by mixing it with an alkali metal dissolved in liquid ammonia; mixing the -alkali metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range oi' 80 C. to about 118 C. to produce a 8alkyl starchate: mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range o! 80 C. to 115 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above 18 C. at 760 mm. pressure with the alkali metal hydroxide supplied in at least stoichiometric quantities to cause a reaction to produce a 2alkali,6alkyl starchate; reacting the 2-alkali-alhl starchate with a non-alkali metal salt in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to produce a 2nonalkali metal. 8- alkyl starchate.

5. A process of preparing a substantially uniformly substituted starch derivative comprising in combination the steps oi substituting an alkali metal atom in place o! the hydrogen atom oi the hydroxyl group of each of a plurality oi' the various units comprising the starch molecule by mixing starch with an alkali metal dissolved in liquid ammonia to form a B-alkali metal starchate; mixing the 6-alkali metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to produce a 6-alkyl starchate; mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range of approximately 80 C. to 115 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above 78 C. at 760 mm. pressure with the alkali hydroxide supplied in at least stoichiometric quantities to cause a reaction to produce a monoalkyl-monoalkali starohate; subsequently reacting the monoalkyl-monoalkali metal starchate so formed by a process comprising mixing it with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to i'orm a dialkyl starchate therefrom in which the substituted alkyl groups on at least two oi' the carbon atoms are diiierent: mixing the dialkyl stai-chate so formed with an alkali metal hydroxide at a temperature in the range oi approximately 115 C. to 118 C. in a substantially nonaqucous alcoholic system in which the alcohol boils at a temperature above 780 C. at '180 mm. pressure with the alkali hydroxide supplied in at least stoichiometric quantities to cause a reaction to produce a polyalkyi monoalkall metal stai-chate; and reacting the starchate so formed by mixing it with an albi halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to form a trialkyl starchate in which the substituted alkyl groups on at least two oi the carbons are diilerent.

0. A process oi producing a substantially unlformly substituted alkyl glucoside which comprises the steps ci reacting starch by mixing it with an alkali metal dissolved in liquid ammonia. and by mixing it with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range oi 80 C. to about 118 C. to produce a 6inonoailryl starchate; mixing the monoalkyl stai-chate so formed with an alcoholic acid solution to eii'ect glucosidic hydrolysis of the stai-chate to produce a -monoalkyl glucoside.

'1. A process oi producing a substantially uniiormly substituted glucoside which comprises the steps of reacting starch by mixingv it with an alkali metal dissolved in liquid ammonia; mixing the 8-alkali metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range oi' 80 C. to about 118 C. to produce a 6-aikyl starchate; mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range of 80 C. to 115 C. in a substantially nonaqueous alcholic system in which the alcohol boils at a temperature above '18 C. at 160 mm. pressure with the alkali metal hydroxide supplied in at least stoichiometric quantities. to cause a reaction to produce a 2alkali.8alkyl starchate; reacting the 2- alkall,8alkyl starchate with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to produce a 2,8-.dialkyl starchate; mixing the dialkyl starchate so formed with an alcoholic acid solution to eiiect glucosidic hydrolysis oi the starchate to produce a 2,6-dialkyl glucoside.

8. The process oi producing a substantially uniiormly substituted polyalkyl glucoside which comprisesthestepsofreactingstarchbymlxingit with an alkali metal dissolved in liquid ammonia; mixing the 8-alkali metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range ot 80 C. to about 118 C. to produce a 6-alkyl starchate; mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range of approximately 80 C. to 116 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above '18 C. at 'i60 mm. pressure with the alkali metal hydroxide supplied in at least stoiohiometric quantities to cause a reaction to produce a 2alkaii.8alkyl starchate; reacting the 2alkali.6

alkyl starchate by mixing it with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range oi.' 80 C. to about 119 C. to produce a 2.6-dialkyl starchate; reacting the dialkyl starchate so formed by mixing it with an alcoholic acid solution to produce by glucosidic hydrolysis a dialkyl glucoside; and esteriiying the glucoside so i'ormed to produce a 2.3.4.6- tetralkyl glucoside.

9. A process of preparing a substantially uniiormly substituted starch derivative comprising in combination the steps of substituting an alkali metal atom in place oi the hydrogen atom of the hydroxyl group oi' each of a plurality or the various units comprising the starch molecule by mixing starch with an alkali metal dissolved in liquid ammonia to form a 6-alkali metal starchate: mixing the 6alkali metal starchate so formed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range ci 80 C. to about 118 C. to produce a 6-alky1 starchate; mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range ot approximately 80 C. to 115 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above 78 C. at 'i60 mm. pressure with the alkali hydroxide supplied in at least stoichiometric quantities to cause a reaction to produce a monoalkyl-monoalkali starchate; subsequently reacting the monoalkyl-monalkali metal starchate so formed by a process comprising mixing it with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to iorm a polyalkyl starchate therefrom in which the substituted alkyl groups on at least two of the carbon atoms are diilerent; hydrolyzing the alkyl starchate so formed by acid hydrolysis; and esterifying the hydrolysis product with an acetyl group.

10. A process of preparing a substantially uniformly substituted starch derivative comprising in combination the steps oi substituting an alkali metal atom in place of the hydrogen atom of the hydroxyl group of each of a plurality of the various units comprising the starch molecule by mixing starch with an alkali metal dissolved in liquid ammonia to form a 6alkali metal starchate; mixing the 6alkali metal starchate so i'ormed with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range oi 80 C. to about 118 C. to produce a B-alkyl starchate; mixing the alkyl starchate so formed with an alkali metal hydroxide at a temperature in the range of approximately 80 C. to 115 C. in a substantially nonaqueous alcoholic system in which the alcohol boils at a temperature above 78 C. at '160 mm. pressure with the alkali hydroxide supplied in at least stoichiometric quantities to cause a reaction to produce a monoalkyl-monoalkali metal starchate; reacting the monoalkylmonoalkali metal starchate so formed by mixing it with an alkyl halide dispersed in a nonaqueous solvent at a temperature in the range of 80 C. to about 118 C. to term a polyalkyl starchate therefrom in which the substituted alkyl groups on at least two of the carbon atoms are difi'erent; hydrolyzing the alkyl starchate so formed; and esteriiying the hydrolysis product.

11. A new article of manufacture consisting ot a substituted glucopyranose polymer, each oi the glucopyranose units o! which has a structural formula of wherein each RI is an alkyl group in which the longest straight chain has not more than tour carbon atoms, each RP is a diilerent alkyl group in which the longest straight chain has not more than four carbon atoms.

12. A new article of manufacture consisting oi a substituted glucopyranose polymer, each of the glucopyranose units of which has a structural formula oi.'

0--1 H R10 CHsgBwH- (CHOGNCHOG') 0- wherein each R1 is an alkyl group in which the longest straight chain has not more than i'our carbon atoms, wherein each G is a cation selected from the group consisting of hydrogen and cations derived irom metal salts and each G is a cation selected from the group consisting of metal cations identical with the cations derived from metal salts comprising G and alkyl groups in which the longest straight chain has not more than tour carbon atoms but which diii'er from R1.

13. A new article ot manufacture consisting oi a substituted glucopyranose polymer, each of the glucopyranose units o! which has a structural formula of 0 H Rl-OCHxlMCH-XCHOH)(0110140150- wherein each R1 is an alkyl group in which the longest straight chain has not more than four carbon atoms, and each Ml is an alkali metal atom.

14. A new article of manufacture consisting oi a substituted glucopyranose polymer. each of the glucopyranose units of which has a structural formula o! wherein each RI is an alkyl group in which the longest straight chain has not more than tour carbon atoms. and each GI is a cation derived from a salt selected from the group consisting o! alkyl ethereal salts o1' which the alkyl group has not more than four carbon atoms and metal salts.

15. A new article of manufacture consisting of a substituted glucopyranose polymer, each of the glucopyranose units of which has a structural formula of 0 H RIOCHIHUJ H) (CHOH) (CBOM) lowherein each R! is an alkyl group in which the longest straight chain has not more than tour carbon atoms, and each M is a metal atom.

KENNETH M. GAVER. DERK V. TIESZEN. ESTHER P. LASURE.

References Cited in the iile oi' this patent UNITED STATES PATENTS Number Name Date 2,397,723 Gaver Apr. 2, 1946 2,518,135 Gaver Aug. 8, 1950 2,572,923 Gaver et al. Oct. 30, 1951 2,609,370 Gaver et al. Sept. 2, 1952 OTHER REFERENCES Muskat: J. Amer. Chem. Soc., March 1934, pages 893-895.

Schmid et al.: Ber.. 68B, 1906-8 (1925) 

1. A PROCESS OF PRODUCING SUBSTANTIALLY UNIFORMYL SUBSTITUTED 2-ALKALI METAL, 6-ALKYL GLUCOPYRANOSE POLYMER WHICH COMPRISES THE STEPS OF REACTING STARCH BY MIXING IT WITH AN ALKALI METAL DISSOLVED IN LIQUID AMMONIA; MIXING THE 6-ALKALI METAL STARCHATE SO FORMED WITH AN ALKYL HALIDE DISPERSED IN A NONAQUEOUS SOLVENT AT A TEMPERATURE IN THE RANGE OF 80* C. TO ABOUT 118* C. TO PRODUCE A 6-ALKYL STARCHATE; MIXING THE ALKYL STARCHATE SO FORMED WITH AN ALKALI METAL HYDROXIDE AT A TEMPERATURE IN THE RANGE OF APPROXIMATELY 80* C. TO 115* C. IN A SUBSTANTIALLY NONAQUEOUS ALCOHOLIC SYSTEM IN WHICH THE ALCOHOL BOILS AT A TEMPERATURE ABOVE 78* C. AT 760 MM. PRESSURE WITH THE ALKALI HYDROXIDE SUPPLIED IN AT LEAST STOICHIOMETRIC QUANTITIES TO CAUSE A REACTION TO PRODUCE THE 2-ALKALI METAL, 6-ALKYL STARCHATE. 